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World Chemicals Sales (2010)
11
400
200
0
1000
800
€ billion
Asia Europe LatinAmerica
OthersNAFTA
Ʃ € 2 353 billion
1147
128
578
455
45
Source: Cefic Chemdata International
1200
600
China
Chemical Industry Sales (2010)Sectoral Breakdown (Europe)
22
Source: Cefic Chemdata International
Basic inorganics13,6 %
Petrochemicals24,0 %
Specialties25,6 %
Polymers24,0 %
Consumer chemicals12,8 %
Large-Scale Catalytic Processes
3
1888 Sulfuric acid production by the contact process
1913 Ammonia synthesis (Haber-Bosch process)
1922 High pressure process for production of methanol
1926 – 1945 Coal liquefaction process for fuel production
1930 Production of synthesis gas for ammonia and methanol
1977 Acrylic acid process
1988 Low pressure production of methanol on the basis of lean gas
1997 Process for decomposition of N2O (greenhouse gas)
2003 High-load process for production of phthalic anhydride
2008 Propylene oxide from propylene and hydrogen peroxide
Heterogeneous CatalystsGlobal Market 2010
4
Polyolefins€ 1,0 bn
Chemicals€ 3,0 bn
Mobile Emissions€ 3,7 bn
Stationary Emissions€ 0,5 bn
Source: BASF estimatesSRI Consulting 2011
∑ € 11,3 bn
ChemicalIndustry€ 4,0 bn35,4 %
Refinery€ 3,1 bn27,4 %
Environment€ 4,2 bn37,2 %
5
Heterogeneous Catalysis (GCC)
New Technologies (GCN)
Chemical and Process Engineering (GCP)
Organic Synthesis and Homogeneous Catalysis (GCS)
Research OrganizationProcess Research and Chemical Engineering (GC)
GCC/CGCC/EGCC/PGCC/S
Major Research Sites for Heterogeneous Catalysis(BASF Group)
6
Beachwood, OH Iselin, NJ
Huntsville, ALShanghai, China
Guilin, China
Nienburg, Germany
Ludwigshafen, Germany
DeMeern, Netherlands
Union, NJ Hannover, Germany
Attapulgus, GA
Numazu, Japan(NECC)
Shihwa, Korea (HCC)
Iselin ShanghaiLudwigshafen
Heidelberg, Germany (hte)Savannah, GA
Vidalia, LAPasadena, TX
Process Research and Chemical Engineering (GC)Research Focus
7
Extension of thevalue chains
Development of newtechnologies
Process optimizationProduct innovation Process innovation
Raw material change
Process Research and Chemical Engineering
Process Research and Chemical Engineering
8
Catalysis
Chem.ReactionEnginee-
ring
ChemicalSynthesis
TechnicalProcess
UnitOpera-tions
Propylene Oxide Product Life CycleTechnologies
11
0
2 000
4 000
6 000
8 000
1965 1975 1985 1995 2005Year
Propylene oxide capacity [kt/a]
Chlorohydrin
MTBE/POSM/PO
Cumene
Total
2010
HPPO
Propylene OxideState-of-the-Art Technologies at BASF
12
Chlorohydrin1930
2.2 t salt/t PO
BASF-HPPOJDA with DOW
2008 water onlyO+ H2O2
- H2O
OH
ClO+ Cl2 + H2O + Ca(OH)2
- CaCl2
OOH
OH
O
+ O2
- H2O
SM/PO1975
2.3 t SM/t PO
Propylene Oxide (HPPO Process)BASF Catalyst
13
Macroscopiccatalyst
CH3O O
SiOSiO
Ti
OSi
O
HH
O+ H2O
Microscopiccatalytic site
+ CH3OH
+ H2O2
Proprietary Ti-zeolite System
Propylene Oxide (HPPO Process)Simplified Process Flowsheet
14
Propylene
H2O2
methanol recycle
pure PO
low boilers
H2O, glycols
pure POoff-gas waterglycols
separation
reactor methanolpurification
crudePO
� Epoxidation using fixed-bed catalyst arrangement
� Full H2O2 conversion and solvent methanol recycle, PO distillation for final purification
off-gas
methanol
HPPOEconomic and ecological advantages300 kt/a Plant in Antwerp
17
� 75% reduction of waste water
� 35% lower energy consumption
� 25% lower capital investment
� Only water as co-product
Recognition of HPPO Technology
18
IChemEAward 2009
York, GB, Nov. 2009
40th KirkpatrickHonor Award 2009
New York, Nov. 2009
US Presidential GreenChemistry Award
Washington, June 2010
Process Research and Chemical Engineering (GC)Research Focus
19
Extension of thevalue chains
Development of newtechnologies
Process optimizationProduct innovation Process innovation
Raw material change
Process Research and Chemical Engineering
Acrylic Acid
20
Colourless liquid with perceptible odour (Tm = 13°C, Tb = 141°C)
� corrosive
� flammable (flash point ~ 49°C)
Acrylic acid, stabilized839
2218
corrosive flammable
CH2 CCHO
HO
Life Cycles of Acrylic Acid Technologies
22
Propylene oxidation
Capacity (Mio. t/a)
4.2
3.6
3.0
2.4
1.8
1.2
0
0.6
1950 1960 1970 1980 1990 2000 2010
4.8
5.4
Cyanhydrin,Acrylonitrile andPropiolactoneprocess Reppe
process
Acrylic Acid from Propene
23
CCHO
HCH2 + 0.5 O2
Acrolein
CHCH2 CH3 + O2
� Process developed by SOHIO and Nippon Shokubai
Bi-Fe-Mo-O
300 - 350 °C
� Since 1977 at BASF
Step 1:
CCHO
HCH2 + H2O
Propene Acrolein∆H = - 341 kJ/mol
Mo-V-O
250 - 300 °C
Step 2:
Acrylic Acid∆H = - 254 kJ/mol
CCHO
OHCH2
Improvement of Acrylic Acid (AA) Catalysts
24
120
110
100
90
67 %
100 %
CO2 Emission / t AA [%] Propene load [Index]AA Yield [Index]
33 %
1976 1981 2001 200619911986 1996
50
200
150
100
50 %
2011
30 %
ElectricityCity with275 000two personshouseholds
Process Research and Chemical Engineering (GC)Research Focus
25
Extension of thevalue chains
Development of newtechnologies
Process optimizationProduct innovation Process innovation
Raw material change
Process Research and Chemical Engineering
26
Light Duty Engine Production (Million)
Source: JD Power, Engine & Transmission Forecast, Q4/2011
2016
102
2015
98
2014
15
66
18
1
60
17
57
17
92
2013
85
2012
77
2011
74
2010
72
2009
57
2008
66
78
23
1
75
22
1
71
20
1
56
16
45
12
51
Gasoline
Diesel
Others
27
Engine out emissions
CO 5,15 0,95 2,79 1,40
Hydrocarbons 1,05 0,16 0,20 0,10
NOx 1,35 0,13 6,78 3,50
Soot Insign. 0,05 0,06 0,03
Gasoline(Audi / 2,0 l)
Diesel(BMW / 2,0 l)
Diesel(MAN / 12,4 l)
Passenger Cars
NEDC
g/km “g/km”
Trucks
g/kWh
WHTC
28
Euro 3
Vietnam
Euro 5Euro 4China
Japan
Global, 4bGlobal, 4aEuro 6
Euro 5
Euro 3
Euro 4Euro 3
Euro 4Euro 3
Euro 3
Euro 4
Euro 5Euro 4Euro 3
Euro 5Euro 4Euro 3
Euro 5Euro 4
Euro 5Euro 4Euro 3
Global, 4bEuro 6Euro 4Global, 4aEuro 5Euro 5Euro 3
Global, 4bGlobal, 4aUS 2010US 2007
CA LEV IIIUS Tier 2, CA
LEV II
201620152014
Euro 6
201320122010
Euro 4
200920082007
India
2011
Thailand
South Korea
Russia
Brazil
Europe
USA
Euro 3
Vietnam
Euro 5Euro 4China
Japan
Global, 4bGlobal, 4aEuro 6
Euro 5
Euro 3
Euro 4Euro 3
Euro 4Euro 3
Euro 3
Euro 4
Euro 5Euro 4Euro 3
Euro 5Euro 4Euro 3
Euro 5Euro 4
Euro 5Euro 4Euro 3
Global, 4bEuro 6Euro 4Global, 4aEuro 5Euro 5Euro 3
Global, 4bGlobal, 4aUS 2010US 2007
CA LEV IIIUS Tier 2, CA
LEV II
201620152014
Euro 6
201320122010
Euro 4
200920082007
India
2011
Thailand
South Korea
Russia
Brazil
Europe
USA
Worldwide Emission Regulations
Light-duty Heavy-duty Motorcycle
Current regulations Future regulations
Phase in
Euro 7 - to be decided in 2016
Main Reactions in Vehicle Exhaust Gas Treatment
30
CO + O2 CO2
Pt / Pd
Hydrocarbons + O2 CO2 + H2OPt / Pd
NOx + CO CO2 + N2
Rh (Pd)
Gasoline engines:
TWC
NO + O2 NO2
Pt
Diesel engines:DOC
NH3 + O2 N2 + H2OPt
AMOX
NO + NO2 + O2 + NH3 N2 + H2OCu/Fe/V
SCR
C + NO2 CO + NO CSF
(1)
(2)
(3)
(1), (2)
(4)
(5)
(7)
(8)
(1), (2), (4)
C + O2 CO2(6)
Vehicles and Catalyst Families
31
Catalysts Applications
Gasoline Engine
LDG TWC
Diesel Engines
LDD
HDD
DOCDOC + CSFDOC + CSF + SCR
DOC + CSF + SCR + AMOX
Motorcycles TWC
Emission Control in Trucks (Euro VI)
32
Diesel Oxidation Catalyst (DOC)
� Oxidation of- carbon monoxide- hydrocarbons
� Oxidation of NO to NO2
Catalyzed Soot Filter (CSF)
� Soot filtration
� Soot burn off
� Oxidation of CO and hydrocarbons
� Oxidation of NO to NO2
Ammonia Oxidation Catalyst (AMOX)
� Oxidation of ammonia to nitrogen
Selective Catalytic Reduction (SCR)
� Reduction of NOx to nitrogen
� Hydrolysis of urea
DOC CSF SCR
Diesel(for soot burn off)
AMOX
Urea
33
General Structure of Automotive Catalysts
Coatings on honeycomb
Exhaust gas
from engineBottom coat
Honeycomb
Top coat
Middle coat
Catalyst
34
Soot-laden gas
Soot-free gas
Gas must filter
through wall
Plug
Porous Filter Wall
Catalyst
General Structure of Catalytic Soot Filters (CSF)
Inlet
channel
Outlet
channelSoot
layer
35
Price ($/tr.oz.)
Year
0
2 000
4 000
6 000
1985 1990 1995 2000
Rhodium
2005 2010
Rhodium Platinum Palladium
Fluctuation of Precious Metal Prices(Average prices p.a.)
Emission Limits and Precious Metal Contentof Light Duty Gasoline Catalysts
36
EURO 1
1992
EURO 2
1996
EURO 3
2000
EURO 4
2005
EURO 5
2009
Ford, Engine displacement ≤ 2 l
Total Hydrocarbons + NOx None Methane Hydrocarbonsg/km g/ft3
0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
0
20
40
60
80
100
120Pt + Pd + Rh
Rh
CO
37
Key Features of Automotive Catalysts
Automotive catalysts have:
� To manage different chemical reactionsat the same time (oxidation and reduction)
� To work under varying reaction conditions
- Low feed concentrations from 100 to 3 500 v ppm but high conversions and selectivities needed
- Rapid oscillations between lean and rich atmospheres
- Temperatures from ambient to 1000 °C
- Space velocities from 10 000 h-1 to 200 000 h-1
� To cope with “other challenges”
Process Research and Chemical Engineering (GC)Research Focus
40
Extension of thevalue chains
Development of newtechnologies
Process optimizationProduct innovation Process innovation
Raw material change
Process Research and Chemical Engineering
Primary Energy Share
41
1850 200019501900 2050
80
60
40
20
0
Primary energy share [%]
TraditionalCoal Gas
Oil HydroNuclear
New RenewablesBiofuels
Source: Royal Dutch/Shell Group, “Energy Needs, Choices and Possibilities“
Syngas to Olefins
42
CO + 2 H2 Kohlenwasserstoffe + H2OReaktion:
Mechanismus:
Produkte: Breite Produktverteilung: C1 (Methan) – C100 (Wachse)
Katalysator
C2H4
Katalysator
C3H6CO
C* C2*
CO
C100*
C100H200CO
CH4CO
C* Katalysator
Methanisierung
C2H6 C3H8
Fe* Katalysator
Wassergas Shift
CO + H2O H2 + CO2
C3*
CO
Benzene from Methane
43
CH4
CHx C2Hy C2+Hz5,5 A5,5 A5,5 A
Mo2C
Zeolite (HZSM-5)
Mo2C
Zeolite (HZSM-5)HZSM-5HZSM-5
Process Research and Chemical Engineering (GC)Research Focus
44
Extension of thevalue chains
Development of newtechnologies
Process optimizationProduct innovation Process innovation
Raw material change
Process Research and Chemical Engineering
PEM Fuel CellProton Exchange Membrane
45
HydrogenHydrogen
HH22 2H2H++ + 2e+ 2e--
Electrolyte(Cell division)
CathodeCathode AnodeAnode
Protons
ElectronsElectrons
AirAir
OO22 + 2H+ 2H++ + 2e+ 2e-- HH22OO1122
WaterWaterWater
Cost Target for Fuel Cell Systems
46
< 1.500 €/kW
< 50 €/kW< 500 €/kW
< 750 €/kw
Car Car -- PEMPEM
Bus Bus -- PEMPEM
Laptop Laptop -- DMFCDMFC BHPP BHPP -- MCFCMCFC
PEMPEM
HomeHome
APU APU -- PEMPEM
Submarine Submarine -- PEMPEM
SOFCSOFC
mobile portable stationary
PEM Fuel CellProton Exchange Membrane
48
HydrogenHydrogen
HH22 2H2H++ + 2e+ 2e--
Electrolyte(Cell division)
CathodeCathode AnodeAnode
Protons
ElectronsElectrons
AirAir
OO22 + 2H+ 2H++ + 2e+ 2e-- HH22OO1122
WaterWaterWater
MOFMilestones by Prof. O. Yaghi (Berkeley)
51
MOF-53,000 m²/g
MOF-1775,000 m²/g
201020041999 Year
SurfaceMOF-210
10,000 m²/g
2009
MOF-2008,000 m²/g
Zeolite 13X
1950
600 m²/g
World record
MOFUnique Properties
52
World record values in surface areastyp. 1 500 - 3 000 m²/g
200 µm
Dead-volume-free structuresin contrast to zeolites and activated carbons
Low solid densities300 - 500 g/l
MOFUnique Properties
54
World record values in surface areastyp. 1 500 - 3 000 m²/g
200 µm
Dead-volume-free structuresin contrast to zeolites and activated carbons
Low solid densities300 - 500 g/l
High thermal stabilitydecomposition only at 350 - 500°C
Variable designmore than 2 000 structures annually
MOFHydrogen Storage Capacities (50 bar, 77K)
55
H2, liq(1 bar, 20K)
COOH
COOH
COOH
COOHHOOC
COOH
COOH
Zn Cu AlZn Zn
2002 20022002 2005
g H2 / ℓTank
H2, gas(700 bar, 298K)
H2, gas(350 bar, 298K)
2007
1417 19
23
33
23
37
71
0
10
20
30
40
50
60
70
80
42
Zn
2009
OHO
O
OHO
OH
COOH
COOH
COOH
COOH
OH
OH
MOFNatural Gas Storage
56
Properties: water-stable, thermally stable up to 350 °C
BasoliteTM A520
Metal: Aluminum
Linker: Fumaric acid
20 µm20 µm20 µmHO2C
CO2H
MOFNatural Gas Storage (Mercedes Sprinter, 295 K)
57
Pressure [bar]
Tank
0
10
40
50
70
60
30
20
0 10 20 30 40 500
100
200
400
300
Methane [gCH4/ ℓtank] Distance [km]
Tank + MOF A520
Customer value: higher distance or lower pressure
MOFNatural Gas Storage
58
Cooperation with
� Agility: US manufacturerof alternative fuel systems
� 1 Truck equipped withMOF A520 pelletsto store natural gas
� Successful operationsince summer 2010